Hydrogenated naphtha soap gels and method of making same



Patented June 22, 19 37 HYDROGENATED NA PHTHA SOAP AND METHOD OF MAKING SAME Carleton cum, Montclair; N. 1., assignor to Standard-I. G. Company No Drawing. Application April 25, 1933. Serial No. 667,830 v 4 Claim.

This invention relates to soap and the process of making same and relates especially to soap gel$, pastes, or emulsions made with the aid 'of petroleum derived products. a

5 The invention is concerned in a specific way with detergents containing hydrogenated or hydrogen-treated petroleum solvents, particularly hydroformed products ranging from the hydronaphthas through the hydro kerosenes and to oils of even higher boiling point.

In co-pending application 658,151, filed February 23, 1933, (Patent No. 2,058,781, granted October 27, 1936) hydrogenatednaphtha soap is disclosed and claimed broadly and the present invention relates to specific improvements over the application referred to.

These hydroformed solvents, or hydrogenolates, are derived from petroleum or its various liquid distillation or extraction products. They may be produced from petroleum distillates, such as burning oil or gas oil, and in general from hydrocarbon oils of a boiling range including that of gasoline and also of ranges extending up to about 650 to 700 F. or somewhat higher. In producing such solvents a petroleum distillate oil may be passed in the vapor phase with free hydrogenover a suitable catalyst at a pressure in excessof20 atmospheres (preferably 50 to 200 atmospheres or higher) desirably at a temperature above 900 F. and preferably within the range of about 930 to 1050 F. with a suitable partial pressure of hydrogen and time of contact to secure reconstituting of the hydrocarbon oil molecules without necessarily forming apprecia ble amounts of polymerized or coky material. The hydrogen supplied is preferably within the range of about 1000 to 4000 cubic feet per barrel of feed oil, the amount generally depending upon the gravity and boiling range of the stock. A 40 greater proportion of hydrogen may be used with suitable variation in feedrate, temperature and pressure. The feed rate depends upon the reaction temperature, and other operating conditions such as the partial pressure of hydrogen. 5 This rate may be suitably about 1.5 to 4 volumes of oil per volume of catalyst-filled reaction-space per hour. The catalysts preferably comprise the oxides or sulfides of the elements of the 6th group together with suitable promoters of the alkaline earth or earth oxides. Such catalysts are substantially insensitive to sulfur poisoning. In the presence of hydrogen they possess the power of hydrunsulfing the petroleum feed stock, thus removing any stench due to the presence of objectionable sulfur compounds.

The hydrcformed petroleum products obtained thereby are mostly characterized by highly desirable solvent powers through their boiling ranges. Ordinarily, however, I prefer to use distillate fractions boiling in a range which lies 5 within the points included between the temperatures of 300 and 550 F., though fractions having an initial boiling point of less than 300 F., or a final boiling point higher than 550 F., are not excluded. Such fractions generally possess 10 rather high flash points and therefore eliminate to a large degree any fire hazard which maybe encountered either during themanufacture of such soap emulsions or gels or during such periods of time they may remain in storage. An example 15 of such a hydroformed naphtha, which is admirably suited for my purpose. is that of the type designated safety fuel, and which may be prepared by subjecting the residues obtained in the distillation of heavy naphtha to a reconstituting process as just described, redistilllng the product .over clay, and retaining the fraction boiling between 313 and 453 F. In one case a product made in this manner was found to exhibit a flash point of 121 F.

One method of making soap gels with these hydronaphthasis to dissolve a soap in the hydronaphtha at a temperature near its boiling point and then allow the solution to cool. On cooling, the solution sets to a more or less stiff mass, de- 30 pending upon the quantity of soap employed.

Soaps which are made by any of the wellknown processes and which contain a low content of water are suitable for my purposes. Such,

soaps are usually produced by the saponifica- 35 tion of tallow or other vegetable or animal fats or oils by means of alkalies, as for example sodium or potassium hydroxide, or by the direct action of such alkalies on the higher fatty acids, as for example stearic acid or distilled cottonseed fatty 40 acids, or on wax acids, or on mixtures of these acids:

I Another procedure for making gels is to grind the soap to a fine powder, and then slowly add hydronaphtha while grinding. The mass slowly 5 sets to a gel, and any desired stiffness or rigidity y can be obtained by regulating the quantity of hydronaphtha used. Still another manner in which these gels may be produced is by dissolving the higher fatty acids, such as stearic, oleic, or 50 distilled cottonseed acids, wax acids, or. mixtures of these acids, in the hydronaphtha, then triturating the solution of acids in hydronaphtha with an equivalent quantity of alkali, such as sodium or potassium hydroxide, dissolved in 55 water. The stifiness of the gels made by this latter process may be regulated by the proportion of acids employed, and consequently the quantity of alkali needed to react with the acids, the proportion of hydronaphtha used, and the volume of wateremployed in dissolving the alkali before causing it to react with the acids. Many combinations of these methods are possible, and in some instances it may be desirable to use such combinations. An example of such combinations would be, incorporating the hydronaphtha with the soap at ordinary temperatures, warming the hydronaphtha soap gel so produced, and

finally cooling to allow it to set to a more solid mass.

If desired, a concentrated emulsion can be formed by adding a small amount of water to the gel composition made as described above. The exact amount of water is not important except in that if too much is used the product will be too thin to set to a gel. In such a case it forms an emulsion paste and if still more water is used a fluid emulsion results. The advantage in mixing a small amount of water with the hydronaphtha soap gel composition is that it facilitates subsequent mixing with water.

Hydronaphtha soap gels made by any of the processes just mentioned may be used as detergents, particularly ior the removal of greases or oils. Such soap compositions are especially applicable as a mechanics soap, or as a soap for the washing of automobiles or other vehicles whose continual use generally results in theaccumulation of grease or oil on certain portions of the body.

A hydronaphtha of the safety fuel type may be converted to a clear jelly-like substance by heating it with as little as 2 to 3 percent by weight of soap. Theclear water-white gelatinized material thus obtained may be employed for cleansing purposes in various ways. Ordinarily, however, I prefer to use a much larger proportion of soap, generally the weight of the soap employed being about 50 percent or more of the weight of the hydronaphtha. Soaps which are made by any of the well-known processes and particularly those which have a low content of water are suitable for my purpose. Such soaps are usually produced by the saponification of tallow or other vegetable or animal fats or oils by means of alkalies, as for example sodium or potassium hydroxide, or .by the direct action of such alkalies on the higher fatty acids, as for example stearic acid or distilled cottonseed acids.

I prefer, however, to use those soaps made by saponifying the wax acids with alkalies, particularly potassium hydroxide, and then drying. Such soaps form jellies which are somewhat darker in color but which are remarkably free from syneresis and therefore better suited for employment in cleansing compounds of this general character than products in which the gel in the some instances Montan wax, by means of strong nitric acid, air, oxygen, or oxidizing gases. Such oxidation is generally carried out at temperatures corresponding to the melting point of the wax or higher (e. g. 300 to 400 F.); and-preferably in the presence of catalysts such as previously oxidized wax, manganese or cobalt resinates,

- possible to use, if desired, perfuming agents in very moderate quantities to yield a perfumed hydronaphtha soap gel. In such instances the perfume maybe dissolved in the hydronaphtha v before it is incorporated with the soap to produce the hydronaphtha soap gel. I

Fillers and/01' abrasives maybe used also. Examples of such substances are pumice powder or silex; also softer materials of the polishing type such'as tripoli or infusorial earths. Another ingredient which could be used is vegetable ivory dust, of which large quantities are available from the button industry. One method of incorporating these fillers and/or abrasives in the hydronaphtha soap gels is to grind the filler and/or abrasive with the soap to a fine powder, and then with constant agitation to heat the powder soap and inert material with suiiicient naphtha so that the soap dissolves but leaves the filler and/or abrasive dispersed throughout the liquid. On cooling, a hydronaphtha soap gel is obtained in which the filler and/or abrasive is suspended throughout. Another method is to incorporate the filler and/or abrasive with powdered soap,

and then while grinding to add slowly the desired term hydronaphtha as employed herein, therefore, should be understood to embrace petroleum fractions of a boiling range higher than that ordinarily comprehended by the term naphtha,

such iractionsfhowever, having a bland sweet odor andv being substantially free from naphthalene derivatives such as Tetralin; the boiling range of the hydronaphthas preferably being in the zone embracing so-called heavy naphtha or light kerosene.

The following examples will serve to illustra the various phases of my invention. The proportions given are parts by weight. 1

Example 1.-2 parts of a commercial white chip soap having a low content of water were ground to a line powder and this powder heated with 100 parts of hydronaphtha, with constant agitation, to approximately 300 F.; when solution had apparently taken place heating was discontinued and the liquid allowed 'to cool. When cold the liquid had set to a clear waterwhite semi-solid mass.

Example 2.--The potassium soaps. of wax acids were prepared by mixing a weighed quantity of the acids with an equivalent quantity of potassium hydroxide, dissolved in water, and removing the water by evaporation. A hydronaphtha soap gel was made, as described by using 2 parts of the dried potassium soaps of wax acids and 10 parts of hydronaphtha. This in Example 1,

el was somewhatdarker in color than that produced in Example 1, and also possessed more I '3' water and the alkaline solution incorporated of a granular'structure.

Example 3.-5 parts of the potassium soaps of wax acids were thoroughly incorporated with parts of hydronaphtha to yield a relativelysolid hydronaphtha soap gel.

Example 4.5 parts 01' the dried potassium soap of wax acids were incorporated with 5 parts of hydronaphtha to secure a hydronaphtha soap gel. This gel was heated toa temperature somewhat below 300 F. and allowed to cool. The granular hydronaphtha soap gel so produced lathered with water and could be used for cleans- 8 P poses.

Example 5.-A somewhat softer hydronaphtha soap gel was made from 5 parts of the dried potassium soaps of wax acids and parts of hyv dronaphtha using the procedure described in Example 4.

Example 6.-The addition of tripoli earth as a filler was made in the following manner. 6

parts of the dried sodium soaps of wax acids -1 part of pumice, as a filler, and 5 parts of hydronaphtha thoroughly L incorporated with the soap mixture. Additional filler, in the ratio 01 4 parts of pumice to 7 parts of hydronaphtha soap gel, was incorporated with the hydronaphtha soap gel. This product was used as a cleansing agent, the relatively large proportion of pumice furnishing a mild abrasive action. 7 Example 8.A white cream-like hydronaphtha soap gel was obtained in the following manner. 5 parts of the sodium soaps of wax acids were thoroughly incorporated with 15 parts of hydronaphtha. 10 parts oi water were then incorporated with the hydronaphtha soap gel.

Example 9.--5 parts or the potassium soaps of 1 wax acids were incorporated with 5 parts of hyample 8.

Example-1 0.--10 parts of wax acids were mixed with 3 parts of hydronaphtha. A quantity of potassium hydroxide sufllcient to react with the waxacids was dissolved in a small quantity of with the hydronaphtha solution of the acids.

' The hydronaphtha soapgel lathered well with water and possessed good detergent qualities.

Example 11.--A filler, such as pumice, was added to the hydronaphtha soap gel as follows: 10 parts of the wax acids were dissolved in 3 parts of the hydronaphtha and 10 parts of safety fuel" and this solution mixed with 10 parts of pumice by grinding. Suiilcient alkali to react with the wax acids was dissolved in a small quantity of water and the alkaline solution thoroughly incorporated with the hydronaphtha, wax acids, and pumice mixture. The hydronaphtha soap gel so produced possessed good detergent qualities.

It is not intended that the invention be limited by any of. the examples which have been given only for illustrative p p ses but it is intended to .claim all inherent novelty in the invention as broadly as the prior art permits.

I claim:

1.'A semi-fluid detergent composition in gel form consisting essentially of a water-soluble soap, incorporated in from about 1, to 50 parts by weight of a solvent consisting of hydrogenated petroleum naphtha boiling within the range from about 300 to about 550 F.

2. A semi-fluid detergent composition consisting of a water-soluble soap incorporated with from about 1 to about 3 parts of solvent consisting of hydrogenated petroleum naphtha boiling Evithin the range from about 300 F. to about 50 F. 3. A method or making semi-fluid detergent compositions which comprises admixing a watersoluble soap with from about 1 to about 3 parts composition which comprises'admixing a watersoluble soap with at least an equal weight of a. solvent consisting of hydrogenated petroleum naphtha boiling within the range from about 300 F. to about 550 F., heating the mixture until the soap is dissolved in the solvent and thereafter cooling the solution.

' CARLETON ELLIS. 

